Composition containing alkyl silane triol and aminoplast resin and article coated therewith



2,937,155 United States Patent ice May 2,937,155 By a durable orpermanent nature, with respect to COMPOSITION CONTAINING ALKYL SILANETRI- OL AND AMINOPLAST RESIN AND ARTICLE COATED THEREWITH John W.Eastes, Ridley Park, Pm, and Richard D. Var- 9 Claims. (Cl. 260-294)This invention relates to a composition comprising water-insolublehydrocarbon silane triols and aminoplast resins, and further to thetreatment of fibrous materials and to the materials so treated.

Various so-called silicone derivatives have been used in the past toimpregnate textile materials for purposes of imparting water repellentcharacteristics thereto. Thus, water-soluble salts of substituted silanetriols have been applied to textile materials for such purposes, butthese require prolonged drying in air, and thus, for the most part, arecommercially not feasible in that few, if any, textile finishing plantsoperate at such low production rates, or have sufficient storage areasavailable for long air drying operations. When a fabric so treated isdried rapidly by heating on conventional equipment, such as tenterframes, followed by a usual process wash, the finished fabric loses itswater repellency.

Silicone derivatives, such as methyl hydrogen siloxane,

have been employed widely in the textile finishing industry for purposesof adding water repellency to textile materials, either alone or incombination with other finish.-

ing materials.

The emulsion of methyl hydrogen siloxane evolves hydrogen and, as aresult, the hazards of fire or explosion tend to restrict its use.

Still further, many of the new water repellent finishes employingsilicone materials impart to the treated fabric a thin hand and othercharacteristics which, in certain instances, are undesirable.

It is an object of the present invention to provide improvedcompositions for imparting water repellent characteristics 'to textilematerials.

Another object is to provide a process for imparting a water repellentfinish to textile materials.

It is a still further object of this invention to provide a waterrepellent composition from which hydrogen is not evolved, and thus thehazard resulting from the evolution of hydrogen in more conventionalsiliconetype water repellent compositions is eliminated.

It is still a further object to provide a water repellent compositionwhich may be applied to textile materials and which may be dried andcured in reasonable periods of time, i.e. times closely related to thedrying and ouring times employed in usual resin finishing operations.

It is still another object of the present invention to provide a textiletreating composition which, when applied to textile materials, willprovide, in addition to durable water repellency, a full hand to fabricso treated, and excellent draping characteristics, as well as othervaluable attributes.

These and other objects and advantages of the. present invention willbecome more fully apparent upon cona water repellent finish, it is meantone which is durable to' both prolonged laundering and repeated drycleaning operations, depending upon the nature of the textile material.

The invention accordingly comprises a composition containing awater-insoluble hydrocarbon alkyl silane triol in which the hydrocarbonalkyl group contains at least 10 carbon atoms, and up to as many as 20,and preferably contains from between 12 and 18 carbon atoms. Used inconjunction with said long-chain alkyl silane triol is a substantiallymonomeric thermosetting aminoplast material that preferably has beenalcohol reacted, which may be either water soluble or water insoluble,which characteristic may be controlled by the size of the alkoxysubstituent(s) thereon. Thereafter, the treated material is dried andthe thermosetting resin cured to a substantially water-insoluble state,employing temperatures in excess of F.

The alkyl silane triols or hydrolyzed alkyl trichloro silanes of thepresent invention may be prepared by hydrolyzing an alkyl trichlorosilane, in which the alkyl group contains from between 10 and 20, andpreferably from between 12 and 18 carbon atoms, in accordance with thegeneral procedure described in US. Patent No. 2,507,200.

Illustratively, these long-chain alkyl trichloro silanes can behydrolyzed to solid silane triol products in water in a variety of ways.Thus, the hydrolysis may be carried out by first dissolving sodiumhydroxide in water, cooling by adding ice, and then gradually adding thealkyl chloro silane with vigorous agitation. The resulting prodnot isthen filtered off, washed with water, and filtered with suction. Thefilter cake may weigh several times the original alkyl chloro silane,due to the water held by the hydrolyzed product.

A typical hydrolyzed material may be used without drying by forming anaqueous dispersion, using either an anionic or a nonionic surface activeagent for emulsification purposes. Or, the hydrolyzed product may bedried at room temperature or in vacuo, in which case a solid, wax-likeproduct results. This solid is soluble in aromatic hydrocarbons such asbenzene, toluene, xylene or their chloro substituted derivatives and thelike, and are believed to have low order molecular weights within therange or about 3300 to about 3900, as measured by the depression of thefreezing point of the benzene solutions.

The aminoplast resin of this invention must be substantially monomeric,and preferably alcohol reacted with lower alkyl alcohols containing from1 to 4 carbon atoms.

, Examples of suitable aminoplast resins, including their alcoholreaction products, are melamine-formaldehyde condensates,guana-mine-formaldehyde condensates, ureaformaldehyde condensates,including cyclic ureas, such as, for example, ethylene urea, 1,2- and1,3-propylene urea, and the like are given. In addition, the alcoholreaction products of succinamide-formaldehyde condensates, adipamide,alkyl thio-bis propionamides, as well as other well-known thermosettingaminoplast materials, are intended to be included.

These thermosetting materials may be used either alone or in combinationwith one another.

Of the above exemplary aminoplast materials, the alkylatedmelamine-formaldehyde condensates and, in particular, alkylatedpolymethylol melamine condensates, are greatly preferred. Thesematerials may contain from 1 to 6 moles of combined formaldehyde andfrom 1 to 6 moles of combined alcohol. The number of carbon atoms in thealkyl groups afiect the solubility characteristics of the alkylatedmethylol melamine. Thus, for example, the methyl, ethyl, propyl methylolmelamines, when substantially monomeric, are substantially watersoluble, while the butylated and higher alkyl materials tend to be waterinsoluble or somewhat hydrophobic.

Depending on whether water, a hydrocarbon solvent, or a mixture of thetwo is employed as the liquid medium of the present composition, thebasic nature of the composition is determined. If the medium is water,and the aminoplast is water soluble, the composition may be generallyclassified as an aqueous dispersion. If a hydrocarbon solvent such asbenzene is employed as the sole liquid medium, the composition will be asolution, in that both of the eseential components are soluble therein.If

a hydrocarbon solvent and water in substantial amountboth constitute theliquid medium, both the essential components may then be principally inthe oil phase or internal phase of the composition or emulsion. Thiswould be true when both the silane triol and aminoplast were waterinsoluble. While such a composition is somewhat more difiicult toemploy, from a point of view of a practical finishing operation, it hasbeen found that the combina tion of the water-insoluble alkylatedmethylol melamine resin with the longchain alkyl silane triols renders afibrous material so treated more durably water repellent than the otherproposed combinations.

The mixture of the silane triol and the aminoplast resin is employed inconjunction with a catalyst, which functions to assist in thepolymerization of the aminoplast during a curing heat treatment.

Suitable catalysts within the meaning of the present invention includeammonium salts, such as ammonium chloride and ammonium sulfate, aminesalts, such as triethanolamine hydrochloride and dilute acids, such asacetic, tartaric, lactic, and the like, and organic or inorganic saltswhich form acids and acid salts when heated at elevated temperatures as,for example, magnesium chloride, zinc nitrate, and the like.

These curing catalysts may be employed in amounts of from between about1 to 60% and preferably from about 2 to 25%, based on the weight of thecurable resin solids of the treating composition employed, which in thiscase is the amount of aminoplast resin employed in the composition.

In a preferred embodiment of the present invention, a compatible surfaceactive agent is included in the composition, which assists and functionsin a composition, in which the liquid medium is in part aqueous, tomaintain a stable dispersion, particularly with respect to the silanetriol content, which would be dispersed in the form of finely dividedsolid particles. In addition, surface active agents enable thecomposition of the silane triol and the aminoplast resin to more readilywet the textile material to which it is applied.

These surface active agents must be non-ionic or anionic in character.Examples of suitable non-ionic surface active agents include thecondensate of stearyl amine with moles of ethylene oxide, which productis known commercially as Ethomeen-18-20; the condensate of hydrogenatedtallow amide with moles of ethylene oxide, commercially known asEthomide HT-25; the condensate of coco fatty acids with 15 moles ofethylene oxide, commercially known as Ethofat C-25; polyethylene glycolmonolaurates, and many others. Examples of suitable anionic types ofsurface active agents which may be used in the present invention areispropyl naphthalene sodium sulfonate, commercially available as AerosolOS; the dihexyl ester of sodium sulfosuccinic acid, commerciallyavailable as Aerosol MA; various sulfated fatty acid esters, and thelike.

Any of the above illustrative surface active agents and equivalentfunctioning surface active agents may be employed singly or incombination with one another. When employed in the composition of thepresent invention, they may be used in amounts of from between 10% up to50% by weight of the silane triol present in the co position.

The aminoplast resinous component of the present composition is employedin an amount of from about 25 to about 1000% by weight of the long-chainalkyl silane triol in the composition, and between about 50 and about500% of the aminoplast with respect to the silane tn'ol resin isrecommended.

If desired, a wide variety of textile-treating additives may beincorporated into the treating compositions of the present invention.For example, softening agents may be added to produce varying handeffects in the finished material. Odor preventatives may be mixed intothe present composition, as exemplified by small amounts of urea ordicyandiamide, which functions to take up any formaldehyde released inthe pad bath or in the curing operation.

While the composition of the present invention is extremely well adaptedto the treatment of cellulosic fabric, as exemplified by cotton andrayon fabrics, the treatment described herein is applicable to anywoven, knitted or felted textile material. This includes fabrics made upin whole or in part of fibers of cotton, viscose rayon, cuprammoniumrayon, cellulose acetate, wool, silk, flax, nylon, of both' theadipamide and caprolactam types, homo and copolymers of acrylonitrile,polyesters such as polyethylene glycol, terraphthalate, etc.

In treating the textile material, a pad bath is the most convenientmeans of uniformly impregnating a textile material. However, sprays andother suitable means such as immersion may be used to apply thecompositions.

Considerable latitude may be exercised in selecting the particularconcentration of solids in the pad bath. For most purposes, a bathcontaining between about 2% and about 40% of solids is recommended. Theadjustment of the squeeze rolls is correlated with the pad bathconcentration in the usual manner, to provide the desired add-on. Withthe novel compositions, these factors should be adjusted to provide anadd-on to the textile material of at least 1% and a practical maximum of25% of the silane triol and aminoplast combined, based on the weight ofthe dry fibrous material. Preferably, the treated material shouldcontain between 0.5 to 5% of the silane triol and 0.5 to 10% of theaminoplast resin.

It is not known for certain whether the treating composition penetratesinto the interior of the fabric or individual fibers, or remains ontheir surface. Thus, the expression contacted, as used herein, isintended to include either deposits of the agents in the interior of thefibers, or on the surface, or a mixture of both.

The treated fabric may be dried and cured in two separate operations, ormay be dried and cured simultaneously. If the former, the material isdried in equipment operating at temperatures of at least F. It isusually preferred to dry and cure in a single operation, in order tosimplify the process. The drying and curing is performed in equipmentoperating at temperatures ranging from between F. and the point at whichdeterioration of the fibrous material commences. In general, thisoperation may be conducted at temperatures between about 200 and 500 F.for periods ranging from between 10 seconds and 30 minutes, with thetime for cure decreasing as the temperature is increased. For mostfibrous materials, the optimum drying and curing is obtained by exposureto temperatures between 250 and 400 F. for a period of between 30seconds and 15 minutes.

In order that the present invention may be more fully understood, thefollowing examples are given primarily by way of illustration. Nodetails therein should be construed'as limitations on the presentinvention, except as they appear in the appended claims. All parts andpercentages are by weight unless otherwise indicated.

In the following examples, reference is made to the following wash anddry cleaning procedures: (1) Sanforized wash test; (2) dry cleaning; (3)process wash; (4) Bendix wash; and (5) rayon wash.

The Sanforized wash test is made according to the procedure outlined inthe test entitled "Dimensional Changes in Textile Fabrics, Cotton andRayon, Standard Test Method 14-52, found on page 132 of the 1952 editionof the Technical Manual and Yearbook of the A.A.T.C.C.

Dry cleaning tests are run in a tumble jar rotating at 55 r.p.m. and ofa 6-liter capacity. Varsol No. H is used as the solvent and 2 liters areused in each test. The samples are rotated for 20 minutes in cleansolvent with this 20-minute period being one dry cleaning cycle. Thesolvent is then removed and replaced by 2 liters of fresh, cleansolvent. This procedure is repeated until a total of three cycles havebeen run. The test swatches are then extracted in a centrifugalextractor, and laid on a flat bed press until dry. They are thenthoroughly steamed to remove any last trace of solvent and pressedlightly to remove wrinkles.

The words process'wash indicate a wash that is given a fabric followinga resin treatment. The sample is passed in open width through a padder,two ends through a solution of 0.1% polymerized ethylene oxide alkylphenol condensation product and 0.1% sodium carbonate, after which itreceives 5 ends through clear water. It is then dried.

The Bendix wash involves washing in an automatic Bendix home washer. Thewash runs for 12 minutes at about 160 F. using 20 liters of water,containing 2 grams Lux soap and 40 grams of sodium carbonate. This isfollowed by three rinses and a final spin-dry.

In the rayon wash, samples are placed in a cylindricaltype reverse washwheel with sample+load to make 3 lbs. Water at 100 F. with soap to makerunning suds (approximately 1.2% soap solution) is used. This is run 15minutes, after which it is stopped, drained, then refilled with water at100 F. and run an additional 5 minutes. Thereafter, the wheel isstopped, drained, refilled, and run minutes. Samples are then extractedand pressed dry. Details of this test appear in the 1950 TechnicalManual and Yearbook of the A.A.T.C.C., page 133, Test Method 40-52.

These tests are run generally in accordance with the standard tests setforth, which correspond to these designations in the 1952 TechnicalManual and Yearbook of the American Association of Technical Chemistsand Colorists.

EXAMPLE 1 6.2 parts of sodium hydroxide was dissolved in 370 parts ofice water. The resulting solution was stirred rapidly while 25 parts ofoctadecyl trichloro silane was added. A white precipitate resulted,which was filtered ofi, washed with water, and drained on a suctionfilter.

12 parts of the hydrolyzed octadecyl trichloro silane, 40 parts of an80% solution of essentially monomeric trimethoxy trimethylol melamine,and 4 parts of a 25% Aerosol OT were intimately mixed. The Aerosol OT isan anionic surface active agent, identified as sodium dioctylsulfosuccinate. 28 parts of this mix were diluted with 170 parts ofwater and 2 parts of ammonium sulfate catalyst was added.

This emulsion was applied to 80" x 80" cotton, so as to add on 3% silanetriol and 8% melamine resin to obtain a water repellent finish durableto both dry clean- EXAMPLE 2 12.4 parts of sodium hydroxide wasdissolved in 1200 parts of ice water. The solution was agitated while 48parts of octadecyl trichloro silane was gradually added. Upon completionof the addition, a resulting white precipitate was filtered oif, washedwith water, and drained on a suction filter for 5 hours. The productweighed 482 parts and contained a substantial portion of the order of10% of octadecyl silane triol- 90 parts of this product and 90 parts oftrimethoxy triing and laundering.

methylol melamine (80% resin solids) and 3.6 parts of a 25 solution ofAerosol OT were mixed together and agitated for a one-hour period. Thismixture was then diluted with water and various catalysts, as given inTable I hereinbelow, were added thereto, in the proportions soindicated. Applications of these dispersions to cotton cloth by paddingto a 100% wet pick-up were made on 9 samples of cloth, as indicated inTable I hereinbelow. This resulted in 8% melamine resin and 1% of theoctadecyl silane triol, based on the dry fabric weight. The treatedcloths were dried for 10 minutes at 175 F. and cured for 5 minutes at300 F. to provide the indicated durable water repellency. In addition tothese properties of water repellency, the treated cloths had excellentdimensional stability and good wrinkle resistance.

Table I A B O Hydrolyzed silsne+melamine resin emulsion parts.. 40. 840. 8 40. 8 (NHOrSO ...do---- 2.0 1.0

Triethanolamine H01 (30% solution) .-.parts-- 4. 0 Water ..--...d0----157.2 158 2 155.2

Total --do-.-- 200 200 200 Cloth Sample No 1 2 3 1 2 3 1 2 3 Sprayratings:

Initial 100 100 90 100 90 90 90 80 90 After one Bendix was 80 80 80After one Santorize was 80 90 80 Aiter3Dry cleanings. 80 80 EXAMPLE 3Simultaneous hydrolysis and dispersion of long-chain alkyl trichlorosilanes were carried out by first dissolving triethanolamine and asuitable long-chain alkyl acid, such as stearic or oleic acid, in hotwater, and then cooling the resulting solution to room temperature. Thissoap solution was agitated while the chloro silane was gradually added.The resulting dispersions were mixed with trimethoxy trimethylolmelamine as given in Table II hereinbelow in the proportions soindicated. The dispersions were applied to cotton cloth by padding to a100% wet pick-up. This resulted in the application of 2% of the silanetriols and 8% of the melamine resin, based on the dry weight of thecloth. The treated fabrics were dried for 10 minutes at 190 F. and.cured for 5 minutes at 300 F. to give a water repellent finish durableto both dry cleaning and laundering.

Table II Hydrolysis Emulsion A B O D Total ..do--..- 861. 1 873.7 889. 3874. 2

Pad Beth Composition:

Above Emulsion .-parts.. 138 144. 6 142. 4 144. 6 solution of trimethoxytrimethylol melamine- ..parts. 20 20 20 20 Water --do.--- 42 35. 4 37. 635. 4

Total .a... zoo zoo zoo zoo Spray Ratings:

Initial 100 100 100 100 After one Bendix wash 90 90 80 Aiter two Bendixwashes... 80 90 90 80 After three Bendix washes- 80 80 80 70 After oneSantorized wash-- 80 80 so 70 Aiter three dry cleanings 70 70 70 50Octadecyl trichloro silane was hydrolyzed and the resultant product wasfiltered and the filter cake dried at between 40 and 50 C. Four parts ofthis product was dissolved in 16 parts of xylene and the solutionemulsified by adding to it, using high speed stirring, an aqueoussolution consisting of parts of Aerosol ND-273, a nonionic emulsifierdescribed more fully in US. Patent No. 2,606,199, and 15 parts of water.This gave a water-inoil system that was inverted to an oil-in-watersystem, by stirring in 60 parts more wtaer. To this was added 20 partsof an 80% solution of trimethoxy methylol melamine, 8.2 parts of a 30%solution of triethanolamine hydrochloride and 71.8 parts of water, andthe resulting dispersion was applied to cotton by padding, dried atminutes at 190 F. and cured 5 minutes at 300 F. to add 2% silane and 8%melamine resin, based on the weight of the fabric.

The treatment imparted a water repellent finish that was durable to bothlaundering and dry cleaning.

The present combination of the hydrolyzed product of long-chain alkyltrichloro silanes in conjunction with thermosetting aminoplast resinshas been found to be particularly effective when a third component isadded to this combination, namely, an alkyd resin. The addition of thealkyd resin (whether oil-free or oil-modified, including short, medium,and long oil-modified resins) provides greater durability to bothlaundering and dry cleamng to fabrics which have been treated therewith.The following example is to illustrate this feature of the presentinvention.

EXAMPLE 5 Octadecyl trichloro silane was hydrolyzed by the generalprocedure set forth hereinabove. This product after drying had amolecular weight of 3940, as determined by the depression of thefreezing point of a benzene solution. It was used to prepare a finishingcomposition as follows:

' Percent Octadecyl trichloro silane hydrolysis product"--- Xylene 60%butylated trimethylol melamine (solution in The 7.5 parts of alkyd resinconsists of 3.75 parts real resin and 3.75 parts of mineral spirits.

The above composition was prepared by melting the chloro silanehydrolysis product and dissolving it in the xylene. This solution wasthen incorporated in a solution of the butylated trimethylol melamineand alkyd resins. In a separate container, 4 parts of the polyethylenetertdodecyl thioether were dissolved in part of the water, after whichthe solvent solution was incorporated into the aqueous non-ionicsolution, using high speed stirring. This oil-in-water emulsion wasfinally diluted with the balance of the water to make up 100 partstotal.

The above product was then made into pad liquors by the followingprocesses: In the first, the pad bath solution consists of parts of thehydrolyzed silane emulsion prepared as hereinabove and 75 parts ofwater. In the second, the pad bath solution consists of 16.6% of thehydrolyzed silane emulsion and 83.4% of water.

Cotton and rayon gabardine were then passed through the above two padbath liquors, giving two dips and two nips, whereupon a wet pick-up ofabout 80% was obtained. This caused the material to have deposited onthe fabric 3% silane triol and 2% silane triol, respectively. Thetreated fabrics were then dried 3 minutes at 225 F. and the cotton wascured for 6 minutes at 300 F. The treated fabric was then processwashed.

The treated materials were then tested for spray ratings after theindicated processing, with the following results:

Table III Cotton Rayon Process Washed 37 29 3 7 27 Benin; Benin souiissou'iis Initial 100 160 100 100 One Sanforlzed wash 100 100 3 additionalrayon washos.. S0

3 dry cleanings 9O 80 80 12 dry cleanings 80 80 80 80 3 rayon w h 100 6rayon washes 90 80 In the composition of the present invention and inthe process for its application to various fibrous and textilematerials, other additives not inconsistent with the performance of thesilane triol or the aminoplast resin and/ or necessary additives such asnon-ionic surface active agents, and/or alkyd resins may be employed. Asexamples, suitable emulsifiers, softeners, lubricants, pigments, dyes,and the like may be used therewith.

We claim:

1. A stable composition for imparting water repellency to textiles whichcomprises a waterlinsoluble alkyl silane triol in which all the alkylgroups contain from 10 to 20 carbon atoms, a lower alkyl alcohol-reactedthermo setting aminoplast resin in an amount within the range of from25% to 1000% by weight of the amount of the silane triol, and from 1 to60% based on the weight of the aminoplast resin of a curing catalyst forsaid aminoplast resin.

2. A composition according to claim 1 which is an aqueous dispersioncontaining from 10% to 50% based on the weight of the alkyl silane triolof an emulsifying agent selected from the group consisting of anionicand nonionic emulsifying agents.

3. A composition according to claim 1 which is an oil-in-water emulsioncontaining from 10% to 50% based on the weight of the alkyl silane triolof an emulsifying agent selected from the group consisting of anionicand nonionic emulsifying agents.

4. An article which comprises a textile material having a durable waterrepellent finish comprising the heatcured reaction product of acomposition according to claim 1.

5. A stable oil-in-water emulsion for imparting water repellency totextiles which comprises a water-insoluble alkyl silane triol in whichall of the alkyl groups contain from 12 to 18 carbon atoms, from between10 and 50% based on the weight of the alkyl silane tn'ol, of a memberselected from the group consisting of anionic and nonionic emulsifyingagents, a lower alkyl alcohol-reacted melamine-formaldehyde resin in anamount within the range of from 50% to 500% by weight of the amount ofthe silane triol, and from 1 to 60% based on the weight of themelamine-formaldehyde resin of a curing catalyst for saidmelamine-formaldehyde resin.

6. An emulsion according to claim 5 in which both the silane triol andthe melamine-formaldehyde components are present in the oil phase.

7. A process for imparting water repellency to textiles which comprisescontacting a textile material with a composition according to claim 1and then heating the textile material so treated above F. to dry andcure said composition to a substantially water-insoluble state, wherebya durable water repellent finish is imparted to the textile material.

8. A process of imparting water repellency to textiles which comprisesapplying to a textile material at least 0.5% by weight of awater-insoluble low molecular weight alkyl silane triol in which all thealkyl groups contain from 12 to 18 carbon atoms and at least 0.5% byweight of a lower alkyl alcohol-reacted melamine-formaldehyde resintogether with a curing catalyst for said resin by contacting saidtextiles with a composition according to claim 5 and then heating thetextile material so treated above 175 F. to dry and cure saidcomposition to a substantially water-insoluble state, whereby a durablewater repellent finish is imparted to the textile material.

9. A stable composition for imparting water repellency to textiles whichcomprises water-insoluble octadecyl silane triol, lower alkylalcohol-reacted thermosetting aminoplast resin in an amount within therange 10 of from 25% to 1000% by weight of the amount of the silanetriol, and from 1 to 60% based on the weight of the aminoplast resin ofa curing catalyst for said aminoplast resin.

References Cited in the file of this patent UNITED STATES PATENTS2,507,200 Elliott et al. May 9, 1950 2,757,152 Solomon July 31, 19562,758,946 Spalding et al Aug. 14, 1956 2,781,332 Swann et al. Feb. 12,1957 2,785,145 Cooke et al. Mar. 12, 1957

1. A STABLE COMPOSITION FOR IMPARTING WATER REPELLENCY TO TEXTILES WHICHCOMPRISES A WATER LINSOLUBLE ALKYL SILANE TRIOL IN WHICH ALL THE ALKYLGROUPS CONTAIN FROM 10 TO 20 CARBON ATOMS, A LOWER ALKYL ALCOHOL-REACTEDTHERMOSETTING AMINOPLAST RESIN IN AN AMOUNT WITHIN THE RANGE OF FROM 25%TO 1000% BY WEIGHT OF THE AMOUNT OF THE SILANE TRIOL, AND FROM 1 TO 60%BASED ON THE WEIGHT OF THE AMINOPLAST RESIN OF A CURING CATALYST FORSAID AMINOPLAST RESIN.